Capturing fleeting intermediates in a catalytic C-H amination reaction cycle

Proceedings of the National Academy of Sciences of the United States of America

Volumn 109, Issue 45, 2012, Pages 18295-18299

  Perry, Richard H ^a   Cahill III, Thomas J ^a   Roizen, Jennifer L ^a   Du Bois, Justin ^a   Zare, Richard N ^a  

^a STANFORD UNIVERSITY   (United States)

Author keywords

C H oxidation; Catalysis; Mass spectrometry; Transient intermediates

Indexed keywords

CARBON; HYDROCARBON; HYDROGEN; OXIDIZING AGENT; RHODIUM;

AMINATION; ANALYTIC METHOD; ARTICLE; CATALYSIS; CHEMICAL REACTION; DESORPTION ELECTROSPRAY IONIZATION MASS SPECTROMETRY; ELECTROSPRAY MASS SPECTROMETRY; IONIZATION; OXIDATION; PRIORITY JOURNAL;

EID: 84868598685     PISSN: 00278424     EISSN: 10916490     Source Type: Journal    
DOI: 10.1073/pnas.1207600109     Document Type: Article

References (37)

1. Zalatan DN, Du Bois J (2010) Metal-Catalyzed Oxidations of C-H to C-N Bonds. Topics in Current Chemistry, C-H Activation, eds Yu JQ, Shi Z (Springer-Verlag, Berlin), Vol 292, pp 347-378.
2. Davies HML, Manning JR (2008) Catalytic C-H functionalization by metal carbenoid and nitrenoid insertion. Nature 451(7177):417-424. (Pubitemid 351181179)
3. 3CN)]. Inorganica Chim Acta 181:7-9.
4. Fiori KW, Du Bois J (2007) Catalytic intermolecular amination of C-H bonds: Method development and mechanistic insights. J Am Chem Soc 129(3):562-568. (Pubitemid 46147756)
5. Zalatan DN, Du Bois J (2009) Understanding the differential performance of Rh2(esp)2as a catalyst for C-H amination. J Am Chem Soc 131(22):7558-7559.
6. Doyle MP, Duffy R, Ratnikov M, Zhou L (2010) Catalytic carbene insertion into C-H bonds. Chem Rev 110(2):704-724.
7. Fiori KW, Espino CG, Brodsky BH, Du Bois J (2009) A mechanistic analysis of the Rh-catalyzed intramolecular C-H amination reaction. Tetrahedron 65:3042-3051.
8. Huard K, Lebel H (2008) N-Tosyloxycarbamates as reagents in rhodium-catalyzed C-H amination reactions. Chemistry 14(20):6222-6230.
9. Müller P, Baud C, Naegeli I (1998) Rhodium(II)-catalyzed nitrene transfer with phenyliodonium ylides. J Phys Org Chem 11:597-601. (Pubitemid 128586745)
10. Nakamura E, Yoshikai N, Yamanaka M (2002) Mechanism of C-H bond activation/C-C bond formation reaction between diazo compound and alkane catalyzed by dirhodium tetracarboxylate. J Am Chem Soc 124(24):7181-7192. (Pubitemid 34633622)
11. Kornecki KP, Berry JF (2011) Evidence for a one-electron mechanistic regime in dirhodium-catalyzed intermolecular C-H amination. Chemistry 17(21):5827-5832.
12. Lin XF, Sun JA, Xi YY, Pang B (2011) Computational interpretation of the stereoselectivity for a dirhodium tetracarboxylate-catalyzed amidation reaction. Comput Theor Chem 963:284-289.
13. 2(II,II)-catalyzed intramolecular amidation of carbamates. Chem Asian J 2(9):1101-1108.
14. Espino CG, Du Bois J (2001) A Rh-catalyzed C-H insertion reaction for the oxidative conversion of carbamates to oxazolidinones. Angew Chem Int Ed Engl 40(3):598-600. (Pubitemid 32146180)
15. Yu XQ, Huang JS, Zhou XG, Che CM (2000) Amidation of saturated C-H bonds catalyzed by electron-deficient ruthenium and manganese porphyrins. A highly catalytic nitrogen atom transfer process. Org Lett 2(15):2233-2236.
16. Cooks RG, et al. (2011) New ionization methods and miniature mass spectrometers for biomedicine: DESI imaging for cancer diagnostics and paper spray ionization for therapeutic drug monitoring. Faraday Discuss 149:247-267.
17. Cooks RG, Ouyang Z, Takats Z, Wiseman JM (2006) Detection Technologies. Ambient mass spectrometry. Science 311(5767):1566-1570.
18. Takáts Z, Wiseman JM, Cooks RG (2005) Ambient mass spectrometry using desorption electrospray ionization (DESI): Instrumentation, mechanisms and applications in forensics, chemistry, and biology. J Mass Spectrom 40(10):1261-1275. (Pubitemid 41552467)
19. Takáts ZW, Wiseman JM, Gologan B, Cooks RG (2004) Mass spectrometry sampling under ambient conditions with desorption electrospray ionization. Science 306(5695):471-473. (Pubitemid 39372443)
20. Perry RH, et al. (2012) Transient Ru-methyl formate intermediates generated with bifunctional transfer hydrogenation catalysts. Proc Natl Acad Sci USA 109(7):2246-2250.
21. Perry RH, Splendore M, Chien A, Davis NK, Zare RN (2011) Detecting reaction intermediates in liquids on the millisecond time scale using desorption electrospray ionization. Angew Chem Int Ed Engl 50(1):250-254.
22. Johansson JR, Nordén B (2012) Sniffing out early reaction intermediates. Proc Natl Acad Sci USA 109(7):2186-2187.
23. Hu QZ, et al. (2005) The Orbitrap: A new mass spectrometer. J Mass Spectrom 40(4):430-443.
24. Perry RH, Cooks RG, Noll RJ (2008) Orbitrap mass spectrometry: Instrumentation, ion motion and applications. Mass Spectrom Rev 27(6):661-699.
25. Roithová J (2012) Characterization of reaction intermediates by ion spectroscopy. Chem Soc Rev 41(2):547-559.
26. Espy RD, Badu-Tawiah A, Cooks RG (2011) Analysis and modification of surfaces using molecular ions in the ambient environment. Curr Opin Chem Biol 15(5):741-747.
27. Xu GM, Chen B, Guo B, He DX, Yao SZ (2011) Detection of intermediates for the Eschweiler-Clarke reaction by liquid-phase reactive desorption electrospray ionization mass spectrometry. Analyst (Lond) 136(11):2385-2390.
28. Coelho F, Eberlin MN (2011) The bridge connecting gas-phase and solution chemistries. Angew Chem Int Ed Engl 50(23):5261-5263.
29. Desikan V, Liu Y, Toscano JP, Jenks WS (2008) Photochemistry of N-acetyl-, N-trifluoroacetyl-, N-mesyl-, and N-tosyldibenzothiophene sulfilimines. J Org Chem 73 (12):4398-4414. (Pubitemid 351842454)
30. Garay J-C, Maloney V, Marlow M, Small P (1996) Spectroscopy and kinetics of triplet 4-methylbenzenesulfonylnitrene. J Phys Chem 100:5788-5793. (Pubitemid 126790445)
31. Gritsan NP, Platz MS (2006) Kinetics, spectroscopy, and computational chemistry of arylnitrenes. Chem Rev 106(9):3844-3867. (Pubitemid 44560459)
32. Yurkovich MJ, et al. (2009) The reactivity of metallated nitrenium ions studied by FT-ICR. Int J Mass Spectrom 287:16-20.
33. Ifa DR, Wu CP, Ouyang Z, Cooks RG (2010) Desorption electrospray ionization and other ambient ionization methods: Current progress and preview. Analyst (Lond) 135(4):669-681.
34. Zhou XG, Yu XQ, Huang JS, Che CM (1999) Asymmetric amidation of saturated C-H bonds catalysed by chiral ruthenium and manganese porphyrins. Chem Commun, 10.1039/A907653K.
35. Benoit F, Holmes JL (1972) Mass spectra of carboxylic acids. 4. Carboxyl-carboxyl interaction in some cycloalkane 1,2 dicarboxylic acids and its relationship with molecular geometry. Org Mass Spectrom 6:541-548.
36. Luo Y-R (2007) Comprehensive Handbook of Chemical Bond Energies (Taylor & Francis, Boca Raton, FL).
37. Girod M, Moyano E, Campbell DI, Cooks RG (2011) Accelerated bimolecular reactions in microdroplets studied by desorption electrospray ionization mass spectrometry. Chem Sci 2:501-510.